Process for purifying hydrocarbon



. 6, 1938. c. o. HOOVER PROCESS FOR PURIFYING I HYDROCARBON OILS 2Sheets-Sheet 1 Original Filed Aug. 10, 1955 INVENTOR Charzs 0. Hoover.

C.- O. HOOVER PROCESS FOR PURIFYING HYDROCARBON OILS Dec. 6, 1938.

2 Sheets-Sheet 2 Original Filed Aug. 10, 1935 c 0 d a $0M Reissued Dec.6, 1938 20,938 rnocnss FOR PURIF I NG nrnnoomon Charles 0. Hoover,Houston, Ten, assignor to Bennett-Clark Co.,'Inc., San Antonio, Tex., a

corporation of Texas Original No. 2,042,050, dated May 26, 1936, SerialNo. 35,652, August 10, 1935. Application for reissue May 25, 1938,Serial No. 209,967. In Canada May 4, 1935 30 Claims.

The present invention relates to a process for the treatment ofhydrocarbon or mineral oils and particularly to the treatment of therelatively light hydrocarbon or mineral oils known as naphthas,gasoline, kerosene, water whites, rafilnate, and the like, for removingor altering "sour compounds, namely compounds which contain sulphur,especially the organic compounds known as mercaptans as well as organiccompounds which may have been formed in the oil by treatment withsulphuric acid or sulphur dioxide or other acid compounds containingsulphur.

The process is especially useful in the case of treating naphthas,rafflnate, gasoline and kerosane and similar like fractions containingsulphur compounds existing in said oils in the form of organic sulphurcompounds and is especially useful in treating naphthas, raffinate,gasoline,

kerosene and similar products containing organic sulphur compounds inthe form of mercaptans, although the process is also applicable to thetreatment of hydrocarbon oils generally which contain said sulphurcompounds.

In general, the present invention relates to process for sweetening sourhydrocarbon oils.

An object-oi the present invention is to provide a process by which thesour compounds in sour oils or distillates may be removed or altered, orconverted into compounds which are not sour, thus rendering the souroils or distillates sweet, and in which process, if desired the agent oragents (other than oxygen) employed to sweeten the sour oils ordistillates may be reactivated or regenerated concurrently with theiruse in the sweetening of the sour oils or distillates, whereby thesweetening of the sour oils or distillates and the maintenance of theactivity of said agent or agents may be efiected at the same time.

A further object of the invention is the provision of a process by whichsour oils may be sweetened without the use of the so called "doctorsolution, that is an aqueous solution of sodium plumbite, and alsowithout the use of aqueous solutions of salts of metals forminginsoluble sulphides with hydrogen sulphide, such as aqueous solutions ofcupric chloride or other cupric salts.

Oils treated in accordance with the process of the present invention arenot only doctor sweet after treatment, but the oils also after treatmentby the process of the present invention frequently show a lowered gumcontent or pass a more satisfactory corrosion test or both. In many'instances also the color and stability of the color of the oil treatedis improved.

The removal of mercaptans from oils of the character described by theuse of doctor solution, or aqueous sodium plumbite solution, is wellunderstood in the art and the removal is accomplished by intimatelycontacting the aqueous sodium plumbite or doctor solution with the oilto be sweetened or from which the mercaptans are to be removed. Thesodium plumbite reacts with the mercaptans to produce lead mercaptidesand these are in turn decomposed by elemental sulphur added to the oiltreatedeither before, after or during the treatment with the doctor orsodium plumbite solution. The elemental sulphur reacts with the leadmercaptides and produces organic disulphides and lead sulphide. Theactual number of grams or pounds of sulphur in the oil combined in theform of mercaptans is not reduced by the treatment with the doctor orplumbite solution, but it is changed into a form that is not sour andrelatively stable; that is, if R represents the organic radicals of themercaptans, the change is from two molecules oi mercaptans, ZRSH, to onemolecule of disulphide, R-SS-R. The plumbite or doctor solution, processof treating sour oils is objectionable in many respects requiringsulphur, large quantities of litharge andcaustic alkali for theproduction of the aqueous sodium plumbite solution and is considerablyexpensive, since the lead of the lead sulphide is lost unless it isrecovered by smelting operations or converted into sulphate or oxide bysome suitable process. The recovery of the leadin available form forreuse is not generally done by refiners, and many refiners, on accountof the cost of recovering the lead in available form from the leadsulphide, find it more advantageous to purchase fresh litharge anddiscard the lead sulphide or sell it for whatever can be obtained forit.

The plumbite treatment is further objectionable in that oils whichbefore treatment exhib ited a satisfactory corrosion test are likelyafter treatment to exhibit an unsatisfactory corrosion test, and theoils treated usually have their total sulphur content increased. I Astill further objection of the plumbite treatment of sour oils is thefact that the insoluble lead sulphide formed in the oil as the result ofthe treatment sometimes settles from the oil very slowly, and dimcultyis frequently experienced in separating the insoluble lead sulphide fromthe sweetened oil.

Sour oils of the character described above when sweetened with aqueousdoctor solution or with water solutions of salts of metals forminginsoluble sulphides with hydrogen sulphide, as for example a watersolution of cupric chloride, when rerun, that is when they areredistilled, produce distillates which are sour to the doctor testnotwithstanding that the oils have been sweetened before distillation byintimate contact with aqueous doctor solution or water solutions of saidsalts. This is an objection which is overcome by the process of thepresent invention, since oils treated in accordance with the presentinvention upon being rerun or redistilled yield distillates which areusually, if not always, sweet to the doctor test.

A further object of the present invention is the provision of a processby which sour oils can be treated and sweetened at a very rapid rate andat a very nominal cost, as the agent or agents (other than oxygen) usedin accomplishing the sweetening action may be regenerated for continueduse, and the oils can be sweetened while flowing at a rapid rate throughthe equipment used.

A further object of the present invention is to provide a sweeteningprocess which includes reactivating or regenerating materials orcompounds after they have been used therein to sweeten sour hydrocarbonoils and distillates.

A further object of the invention is the sweetening of sour hydrocarbonoils by a process in which the reagents employed, other than theoxygen-containing gas, are in solid form, thereby avoiding theobjectionable corrosion of the equipment and the formation of suspensionin the oils undergoing treatment, which often occur where the reagentsfor sweetening the oils are employed in the form of aqueous or othersolutions or suspensions.

According to the present invention mineral or hydrocarbon oils, forexample gasoline, naphthas, raflinate, water whites, furnace oils,Diesel engine oils, transformer oils, kerosene, or heavier oils thanthese, containing mercaptans or other sour constituents, which are to besweetened, are brought in intimate contact with a compound of a metal insolid form which, even at atmospheric temperatures, will enable the souroil to be sweetened, which metal compound has the further property ofbeing able to be revivified or regenerated, for repeated use in enablingthe sweetening of sour oils by contacting it with oxygen or an oxygencontaining gas, for example a compound of a metal which may be reducedfrom. a higher to a lower valency. This intimate contact is preferablyaccomplished in the presence of a solid adsorbent material, for example,clay of a highly adsorbent character, such as fuller's earth orbentonite or like clays, or in the presence of other material havingadsorbent properties such as alumina, or activated alumina. Examples ofspecific metal compounds which may be employed are cupric oxide, cuprichydroxide, cupric chloride, cupric nitrate, basic cupric carbonate,mercuric chloride, ferric chloride, ferric sulphate etc. Iron compoundsusually give objectionable colorations to oils containing a highproportion of unsaturated hydrocarbon compounds and for that reasonwould not be used in treating such oils" when an uncolored product isdesired. Cupric chloride may advantageously be used in treatingnaphthas, raffinate or gasoline or other oils containing highproportions of unsaturated hydrocarbon compounds. In addition to theadsorbent and metal compound an oxidizing agent may be associatedtherewith such as alkali permanganates, as potassium permanganate ormanganates, manganese dioxide or other oxidizing agent. According to thepresent preferred mode of practicing my invention the metal compounds,such as c'upric oxide, cupric hydroxide, cupric chloride, cupricnitrate, basic cupric carbonate, mercuric chloride, ferric chloride orferric sulphate etc'. are kept active or regenerated by intiniatelymixing with the naphtha or gasoline, or other oil to be treated, air oroxygen, or an oxygen containing gas or an oxidizing agent either solidor liquid capable of oxidizing the metal in the metal compounds from thelower to a higher valency, but I do not limit myself to this specificmanner of accomplishing the said regeneration, as other modes ofaccomplishing the regeneration are within my invention, as more fullyset forth below.

Very satisfactory results may be obtained by utilizing a mixturecomprising from '70 to 98 per cent clay with from 30% down to 2%, and

even less, of metal compound as for example cupric chloride. Anoxidizing agent may be mixed into the mixture. of clay and metalcompound to the extent of about 2-15%, for example of potassiumpermanganate. When the form of apparatus shown in Figure 1 of theaccompanying drawings (which is hereinafter more particularly described)is used to practice the invention, the reagents in the mixture,including the clay or other adsorbent, preferably should be in a linestate of division, preferably completely passing through a 100 meshscreen and most of it passing through a 200 mesh screen. However, whenthe form of apparatus shown in Figure 2 of the accompanying drawings(which is' hereinafter more particularly described) is used to practicethe invention, the metal compounds and clay or other adsorbent may beused in a very much coarser state of division, for example of to meshscreen size and even larger. Very satisfactory results are produced byusing a reagent mixture containing 90% of dry clay, 5% of cupricchloride and 5% of potassium permanganate. A satisfactory mixture alsoconsists of 95% dry clay and 5% solid cupric chloride. The mixtures ofadsorbent material and metal compound, or mixtures of adsorbentmaterial, metal compound and oxidizing agent are used in a dry orsubstantially dry condition, such as may be obtained by mixing thedivided dry adsorbent material and the divided dry metal compounds ofthe kind'indicated above, or by mixing the divided dry adsorbentmaterial, the divided dry metal compounds and the divided dry oxidizingagent. The mixture of metal compounds and adsorbent materials may alsobe prepared by impregnating the adsorbent material with a solution ofthe metal compound or compounds and thereafter evaporating the solventof said solution. ,For instance, the adsorbent material may beimpregnated with a water solution of cupric chloride to the extentnecessary to produce the proportion of cupric chloride in the adsorbentdesired, and thereafter the so impregnated adsorbent material dried toevaporate the water of solution, but leaving preferably the water ofcrystallization in the solid cupric chloride resulting from theevaporation of the water; or the adsorbent material may be impregnatedwith a solution of cupric chloride in methyl alcohol noses metalcompounds or oxidizing compounds is not objectionable. The presence of aslight amount of water is not particularly disadvantageous, but theamount of water should not reach such an extent as to form anindependent solution phase separable or flowable as such from theadsorbent material, or as to form an aqueous muddy mass with'the clay orother adsorbent. Practical limits to which water may be present in thepractice of the process are considered below.

Thus, in the beginning of the practice of the invention the metalcompounds are present in association with the clay or other adsorbent inthe solid and substantially dry condition and the clay or otheradsorbent is also substantially dry, but the water moisture content ofthe metal compound and/or clay or other adsorbent may rise considerablyabove absolutly anhydrous conditions, or air dry conditions, withoutimpairing the operation of the process, and for example,

the .water moisture content of the solid mixtureof metal compound andadsorbent material may rise to to 25 per cent or more, depending, moreor less upon the nature of the adsorbent material and its state ofdivision.

According to one manner of practicing the in ventlon, and utilizing clayas an example of the adsorbent material used, the metal compound ormixture of metal compound and clay, with or without added oxidizingagent, may be agitated in any suitable way with the sour oil, naphthasor gasoline etc., and air or oxygen intimately contacted with the massbeing agitated. After agitation of the naphthas, gasoline or keroseneetc, in presence of air or oxygen and the metal compounds or metalcompounds and clay, the metal compounds and clay are allowed to settlefrom the sweetened naphthas, gasoline or kerosene, etc., and the saidsettled metal compounds, or metal compounds to ether with the clayassociated therewith, are again agitated with another quantity of sournaphtha, gasoline or kerosene, etc.,

in the presence of air or oxygen to produce sweetening of the oils.

In carrying out the use and re-use of reagents in this modification ofthe invention, the reagents, sour naphthas, gasoline or kerosene, etc.,and air, or oxygen, may be fed to the inlet of a centrifugal pump whichwill produce the necessary agitation of the oils, reagents and air oroxygen. The oil will be substantially completely sweetened on passingthrough the centrifugal pump. The mixture may then be led to a pointabout midway of the height of a tall tank where the reagents and claywill settle from the sweet naphthas, gasoline or kerosene etc. Thereagents and clay with some oil may be aspirated from the bottom of thetank by the centrifugal pump and fed with further quantities of sournaphthas,

gasoline or kerosene etc., and air or oxygen to the inlet of 'thecentrifugal pump and the mixture produced by the pump discharge into thetank as above described. Sweet oil will accumulate in the upper portionof the tank free of metal compound and clay, and may be drawn oficontinuously or intermittently. The centrifugal pump may be operatedintermittently or continuously in its aspiration of reagent and clayfrom the tank and in its mixing of the reagents and air or oxygen withthe sour oil and discharging of the mixture into the tank.

I have found it advantageous, in some instances,

' ious pipes.

to add a small amount of an acid to the oil undergoing treatment. Theacid is preferably one which contains the negative radical of the metalcompound. Thus in the case of cupric chloride .it would be hydrochloricacid, in the case of cupric nitrate it would be nitric acid, andsulphuric acid forsulphates. This addition of acid in many casesvincreases the degree and rate of regeneration. This additional acid isrequired in those cases where on account of the acidic character of thesalt or metal compound in the presence of water or moisture, acid isremoved by reaction with basic constituents of the clay or adsorbentemployed or adsorbed as acid by the clay or other absorbent. Asunderstood by the person skilled in the art, the amount of acid to beadded will depend upon a number. of factors including the character ofthe clay or other adsorbent and the degree of hydrolysis of the salt,all of which may be readily ascertainable, if not by computation, thenby trial.

The drawings accompanying the present application show schematically twoforms of apparatus suitable for use in practicing the invention, Figure1 showing one form of apparatus, and Figure 2 another form of apparatus.

Referring to Figure 1 of the drawings the numeral I indicates acentrifugal pump. vThe numeral 2 indicates a settling tank. Thedischarge end of the centrifugal pump I is connected with the settlingtank 2 by means of a'pipe 3, the pipe 3 discharging into-the tank 2about midway of its height. The numeral 4 indicates a line from whichthe sour oil to be treated is taken. The tank 2 is conically shaped atits bottom and discharges from its bottom into a pipe 5 which connectswith a pipe 6 which leads to the inlet side of the centrifugal pump I,the pipe 6 forming acontinuation of the pipe 4. A hopper I is con nectedby means .of a pipe '8 to the pipe 6 for introducing into the pipe 6 themetal compound or adsorbent and metal compound mixtures described above.A pipe-9 connects with the pipe 6 for introducing air or oxygen into'thepipe 6 leading to the inlet of the centrifugalpump I.

' The air or oxygen is preferably dry. Hydrochlo- II may be connectedwith the pipe {to discharge oil into the'hopper I to facilitate thedischarge of absorbent and reagent from the hopper 1 into the pipe 6 Tothe upper end of the tank 2, or near its upper end, is connected adischarge pipe I2 for the treated product. may be connected with thedischarge pipe I2 to removeany entrained metal compound, adsorbent orsuspended matter in the oil treated. This strainer is not usuallynecessary, since if the outlet of the tank 2 for the pipe I2 issufliciently high above the discharge point of the'pipe 3 into the tankand if 'the discharge outlet of the pipe 3 is sufliciently large to slowdown sufficiently the velocity of the oils entering the tank, theadsorbent and metal compound will completely settle from the oils beforethe oils are discharged through the pipe I2. The numeral I4 indicatesvalves for suitably controlling the flow in the var- A pipe I5 alsoconnects with the discharge from the centrifugal pump I, the purpose ofsaid pipe I5 being to enable the system or apparatus to be emptied.

In operation the sour oil to be treated enters from the pipe 4 into thepipe 6 where it is mixed with air entering the pipe 6 fromthe pipe 9.

A strainer or filter I3 1 Where an acid is to be used, the same may beintroduced through the pipe Ill. The metal compound or mixture of metalcompound and absorbent clay enters thepipe 6 from the hopper 1 by meansof the pipe 8. In this description of the operation, a mixture of 95%clay and 5% solid cupric chloride is taken as illustrative of thereagents employed. The sour oil, substantially free of undissolved water'(that is without admixture with water), and preferably dried by passageover rock salt (NaCl) or calcium chloride, is intimately mixed with theair and clay-cupric chloride mixture in the centrifugal pump l and themixture is discharged through the pipe 3 into the tank 2 where theclay-cupric chloride mixture settles from the oil in the conical portionof the tank 2. The settled clay-cupric chloride mixture with some oil isthen redrawn into the pipe 6 through the pipe 5 under the action of thepump for treating further quantities of sour oil. a

The treated or sweet oil is withdrawn from the tank 2 by means of thepipe l2, and, if necessary,

and the sweetened oil withdrawn through pipe IL.

The sweetening is substantially fully accomplished after the mixture ofoil and reagents has passed through the centrifugal pump I. I

As the oil to be treated enters the circulating body of oil and reagents"from the pipe I, the treated oil is withdrawn through the pipe H. Theclay-cupric chloride mixture is thus continually re-circulated with oilto be treated.

The clay-cupric chloride mixtureseems to be utilizable in the form ofapparatus shown in Figure 1, as long as it is practically possible tocirculate it with the oil undertreatment. The conversion of themercaptans into doctor sweet products is accompanied by the .formationof very small amounts 01 water which appears to be taken up by the claymixture together with water or moisture associated with the air, dryhydrochloric acid, or oil fed into the apparatus as described. It hasbeen found that when the moisture content of the 'clay mixture reachesabout .10 to 14 per cent, small spherical pellets are formed in theapparatus shown in Figure l, the said pellets then being considerablysmaller than mustard seed.

The air, oxygen, or oxygen containing gas, which is used to regenerateor reactivate the metal compounds or mixtures used to sweeten the souroils, also acts to considerably retard the formation of these pellets.The air or oxygen or oxygen containing gas also prevents certainobjectionable colorations from occurring in the oils treated which wouldotherwise be the case it oxygen were not used. This is especially truewhere cupric salts or mixtures of cupric salts and adsorbents areemployed, for example a .mixture oi 95% the settled clay mixture in thetank 2 may be withdrawn by pumping it out through the pipe l6, and theso withdrawn clay mixture, which is in the form of a slurry with oil, issubjected to a drying operation in order to reduce the moisture or'water content, whereupon the clay mixture may be used again for treatingfurther quantities of oil until the water concentration builds up againto an objectionable degree, after which the clay mixture may be againfreed of moisture or waterby drying and used over again.

The drying of the clay mixture slurry may be accomplished by spreadingthe slurry out in thin layers and permitting the oil and moisture toevaporate, either with or without the application 01 heat. When treatingraflinates, the slurry of raflinate and clay mixture is advantageouslydried by distillation under reduced pressure at a temperature preferablynot exceeding 200 F. The vacuum employed with this temperature is about28 inches or an absolute pressure of 1.92

inches.- Heat and vacuum may be similarly applied to dry the claymixtures when used to sweeten other oils besides rafllnates.

Instead of agitating the sour oils tobe treated with the variousreagents employed. as in the use of the apparatus shown in Figure 1, thecontact between the reagents and the sour oil-may be accomplished bypassing the oil and an oxygen containing gas through one or morestationary beds of solid reagents or mixtures, as illustrated in Figure2.

Referring to the form of apparatus shown in Figure 2 or the drawingswhich can be advantageously used in practicing the invention andutilizing cupric chloride and iiillers earth-as examples of the metalcompound and adsorbent material used therein, the numeral 26 indicates adrum containing a mass 21 of rock salt (NaCl) or other drying agent,such as solid calcium chloride, for extracting water moisture from thesour oils to be sweetened or treated. These drying agents 2'l aresupported within the drum 26 by means of a grid, screen or perforatedplate 26 which extends across the drum 26 near the lower end butabovethe inlet pipe 29 for the sour oils to' be sweetened. .Prior tointroduction into the drying drum 26, the sour oil or oils preferablyarefreed oi hydrogen sulphide as by intimate contact with a water solutionof sodium hydroxide or other agent. Also prior to introduction of thesour oil into the drum 26, it is advantageous to let as much water aspossible settle from the oil by gravity, so as to avoid unnecessaryburden on the drying agents '21, and to increase the general efllciencyot the process. The sour oils rise through said drying drum 26 and comeinintimate contact, in their passage through said drum, with the rocksalt, or other drying agent, contained in said drum. The dried, hydrogensulphide free, sour oils pass out of said drum by means of a pipe 30which leads to thelower part of the treating chamber or container 3|.The lower end of the drying drum 26 is provided with an outlet 32controlled by 'a valve 33 for exhausting accumulated water or saltsolution from the drum 26,

I A steam actuated pump designated generally by the numeral 34, andsupplied with steam from asteam line 36, removes from the pipe 30 aportion of the sour oil flowing therein. This removal of oil from thepipe 30 is accomplished through a pipe 36 connected between the pipe 30and the pumping chamber of the pump 34. The portion of the oil thusremoved by the pump 34 is delivered by the pump through the pipe 31 tothe ejector 33, into which ejector leads a valve controlled pipe 33 forthe introduction of regulated amounts of dry oxygen, or air, or a drygas rich in oxygen, into the ejector for incorporation into the oilpassing through said ejector. The introduction of the regulated amountsof oxygen may be continuous or intermittent. The oil and oxygen leavingthe ejector 38 pass, in the form of a mixture of oil and oxygen, 'intothe pipe 43 and then into the pipe 30, where the mixture of oil andoxygen delivered by the pipe 4|! mixes with the main body of sour oilflowing in the pipe 33. The pipe 40, as shown, connects with the pipe 30at a point nearer the treating chamber ll than the point of connectionof the pipe 36 with the pipe 30. In the steam line 35, is indicatedgenerally by the numeral 4| a governor for.

the pump.

A section 42 of the pipe 30, between the point where the pipe 40connects with the pipe an. and the treating chamber 3|, is occupiedadvantageously by an orifice mixer. or othersuitablemixer,

for intimately mixing the oil and oxygen or air before it passes throughthe remaining portion 43 of the'pipe 30 and enters the lower part of thetreating chamber 3|.

The treating chamber 3| is provided with an outlet 44 for the sweetenedoil at the top of said chamber, and a drain outlet", controlled by thevalve 46, at the bottom of said treating chamber. In normal operation,the valve 46 is closed. The outlet 44 is connected with a coupling 41,one branch of which is connected with the pipe 48 for conducting thesweetened oil to storage and another branch of which is connected withthe safety valve 43. A grid, screen, perforated plate or porous earthenor refractory plate 53 extends across the chamber 3| nearer the lowerend than the top and above the inlet for the oil for supporting themetal compound and adsorbent material 5| within the chamber.

The cupric chloride and fuller's earth, used as specific examples ofmetal compound and adsorbent material, in describing the apparatus shownin Figure 2 and its operation, may be disposed within the chamber 3| indifferent ways. For example: (1) A more or less intimate mixture ofsolid cupricchloride and fullers earth may be previously formed andintroduced into the chamber 3| and distributed as a more or less uniformlayer above the supporting member (2) the solid cupric chloride andfullers earth may be introduced into the chamber 3| separately andmoreor less simultaneously, for example by introducing solid cupric chlorideand fullers earth separately and simultaneously in the desiredproportions into the chamber 3| until the desired amount of both isintroduced, the mixing occur- 'of cupric chloride and fullers earth maybe placed upon the member 50 and a layer of fullers earth placed overit; (6) several layers of solid cupric chloride and fullers earth may beused alternating with eachother; ('7) a layer of,

fullers earth maybe placed upon the supporting member 50 and upon thislayer is placed a layer of solid cupric chloride or a layer of a mixtureof solid cupric chloride and fullers earth, and over these layersanother layer of fullers earth followed by another layer of solid cupricchloride or a mixture of solid cupric chloride and fullers earth. In allof these and in other arrangements of materials it is advantageous tohave an uppermost layer either of fullers earth, or other suitableabsorbent, or a mixture of fullers earth (or other adsorbent) and cupricchloride. The necessary thickness of the layers of reagents upon thesupporting member 50 may be readily ascertained by trial and ordinarilyno trouble is experienced in this regard. The rule to follow in regardto the amount of reagents and thickness of layers of reagents is thatsufficient reagents and suflicient thickness of layers must be employedso that the oils passing out of the chamber 3| through the pipe 48 shallbe .sweet, or sweet to the desired extent and sub- ,stantially free fromorganic sulphur metal com- 33 which leads into the treating chamber 3|.

While the main body of the sour oil is proceeding to the treatingchamber 3|, a portion of the sour oil is removed from the main stream"through the pipe 36 and is then mixed with oxygen in the ejector 38 andre-inserted into the main body of the oil flowing in pipe 30, whereintimate mixture of the oil and oxygen occurs before the mixture isintroduced into the treating chamber 3 I. The oil and admixed oxygenthen pass through and in contact with the cupric chloride and fullersearth, and the sweetened oil passes out of the chamber 3| by means ofthe pipes 44 and 43.

the apparatus, and is withdrawn as sweetened oil through the pipe 48 asfast as sour oil enters the pipe 29. The sour oil mixed with the oxygen,therefore, is caused to pass rapidly through the body of reagents 5|within the treating chamber 3|.

When the process is practiced in the apparatus shown in Figure 2, theformation of the'pellets, encountered in the practice of the process inthe apparatus shown in Figure 1, does not occur. Due in part to thisfact and to the employment of a stationary bed of solid reagents, thelatter are highly eilfective for removing the constituents impartingsourness to these oil s, even when the solid reagents have moisturecontents as high as 20 or 25% of their own weight, under the conditionsheretofore described. Solid reagents containing around 15% of moisturehave been used continuously for the sweetening of over. one and a halfmillions of barrels of sour pressure ulstillate in accordance with thepresent invention,

without measurable decrease in the efficiency of the said reagents.

Another feature of the present invention consists in the use ofregulated small amounts of oxygen-containing gas (preferably pure oxygenor oxygen-enriched air) in the process and apparatus above described. Byregulating the small quantities of oxygenwill sweeten the sour oils andconcurrently maintain the activity of the solid reagents. Since theserelatively small amounts of oxygen are added to the oils undergoingtreatment, and since preferably the treatment of the oils is conductedat or not greatly above atmospheric temperatures, there is little, ifany, oxidation and destruction of unsaturated Hydrocarbons contained inthe oil. Therefore, the use of only so much oxygen as'is necessary toaccomplish the sweetening of the oil and to maintain the activity of thesolid reagents results in sweet oil having a lower content of gums orgum forming substances than such oil would have if the oxygen had beenindiscriminately used or used in excessive amounts. The regulation ofthe amount 01' oxygen entering the apparatus shown in Figures 1 and 2may be accomplished by any suitable valves or gas regulating meansapplied to the pipes 9 and 39.

In the above described processes of treating -mineral oils, finelydivided kieselguhr, pumice,

calcium silicate, porous earthenware, and sand may be substituted in'whole or in part for the clays and other adsorbent materials abovedescribed. Other adsorbents such as active (or acti-- Vated) carbon orsilica gel may be substituted in whole or in part for the adsorbent oradsorbent clays or alumina or activated alumina heretofore mentioned,and all of these adsorbent materials are utilizable in about the sameproportions.

The gasoline or other oils containing mercaptans or other organic sourconstituents are sweetened by treatment according to the presentprocess. The mercaptans which are the principal sour constituents arechanged into organic disulphides of the type R-S-SR in the sweetasoline. As a result of this conversion of mercaptans into disulphides,acid (as hydrochloric acid when using cupric chloride) appears to arisewhich would otherwise be found present in the treated gasoline or otheroil were it not for the presence of the adsorbent which appears toretain the acid and prevents it from contaminating the sweetenedmaterial. The clay has the further action of retaining the acid so thatit may be present in contact or in association with the metal I compoundso that the oxygen or air used to accomplish the regeneration may betteraccomplish its function. The organic disulphides arise because of theoxidation of the mercaptans in the sour oils to disulphides and water,which small amount of water either remains in solution in the oiltreated or is taken up by the clay. This oxidation action, wherepolyvalent metal compounds are employed, is accompanied by a reductionin the valency or degree of oxidation of the metal, which is restoredagain to a higher valency or maintained in a higher valency or state ofoxidation by the air or oxygen which is introduced into the apparatus,The chemical actions taking place in the process utilizing a metalcompound, an adsorbent and oxygen, air or other equivalent oxidizingagent will more fully appear from the following explanations, usingcupric chloride, fullers earth and oxygen, respectively as the metalcompound, adsorbent and oxidizing agent: the cupric chloride reacts withthe sour constituents (the mercaptans) and forms therewith coppermercaptides (organic sulphur metal compounds) and becomes spent to theextent that it has reacted with the sour constituents:

these mercaptldes (organic sulphur metal compounds) are removed from theoil, or caused to disappear therefrom by the action of the fullers earth(the adsorbent material), and the oxygen which is added over and aboveany naturally occluded in the fuller's earth (adsorbent material)maintains, renews or continues the activity of the cupric chloride(metal compound) to sweeten the sour oil, that is to say regenerates whatis spent, as well as continues or maintains the activity of the fullersearth (adsorbent material) to remove or cause the disappearance ofmercaptides (or-.

ganic sulphur metal compounds). The net result of the actions may,therefore, be considered as carrying of oxygen to the mercaptans or sourconstituents to oxidize them.

compounds used in their higher valency conditions. An excess of air oroxygen appears to be without harmful influence on the treatments of theoils, except that excesses of air or oxygen promote the formation ofgums in oils containing unsaturated hydrocarbons. For example, in thecase of cupric chloride enough air or oxygen must be used to keep thecupric chloride in the cupric condition. It is generally preferable inthe practice of the invention, where oxygen is used as the oxidizingagent, to employ .01 cubic foot of oxygen per barrel of 42 gallons ofhydrocarbon distillate for each milligram of mercaptan sulphur presentin each 100 c. c. of the distillate. However, in instances where the oilor distillate has been given the usual sulphuric acid treatment prior tothe present sweetening process, two or more times this amount of oxygenmay be employed without detrimental results; and like excesses of oxygenmay be employed when treating straight run distillates without formingobjectionable amounts of gums or gum forming compounds. when, however,considerably larger percentages of oxygen, or the equivalent of oxygencontaining gas, are employed in the process in treating oils containingunsaturated hydrocarbons, gum formation occurs and substantial amountsof valuable hydrocarbons are lost. When dry hydrochloricacid gas isused, it is used in sufiicient quantity to make up any loss ofhydrochloric acid from the cupric chloride. In the specific examplesgiven above, the hydrochloric acid gas added may amount to about 0.01cubic foot dry hydrochloric acid gas per barrel of oil treated, althoughthe amount of 'acid may exceed this amount. The excess of acid cess ofhydrochloric acid is not'harmful, but on the contrary is beneficial,improving the color and color stability of the sweetened 011.

In cases where the oil or material to be treate contains considerableamounts of hydrogen sulphide in addition to the mercaptans, it ispreferable to intimately contact the material with an aqueous causticsoda solution, or any other suitable agent, for the purpose of removingthe hydrogen sulphide. In the case of treating naphthas, gasolines orkerosenes etc., as now prepared by refineries, it is not usuallynecessary to employ this caustic alkali treatment as a preliminary stepto the process of the present invention, for the reason that thenaphtha, gasoline or kerosene etc., is usually, during its preparationor manufacture by the refineries, intimately contacted with a watersolution of sodium hydroxide which would remove hydrogen sulphide andcompounds of a kindred nature.

The hydrocarbon oils are treated according to the present invention inliquid phase, the treatment being advantageously performed atatmospheric temperatures, at which temperatures the reagents (such ascuprlc chloride etc.) would normally react with mercaptans to formmercaptides and which temperatures are below the point at whichmercaptides would be decomposed by heat; although it is to be understoodthat the present invention also applies to oils which may be heated to apoint considerably above ordinary atmospheric temperatures but belowtheir boiling points. The oils also may be treated under pressure eitherat atmospheric temperatures or higher temperatures indicated above. Itis a well known fact that hydrocarbon or mineral oils and distlllatesthereof are usually stored or collected in large tanks in the open andsubject to all changes in atmospheric temperatures, and the termsatmospheric temperatures or "atmospheric temperature" as used herein areintended to include temperatures within the range of temperatures towhich such oils and distillates may be subjected while contained intanks exposed to the atmosphere. H

The invention may be applied to the treatment of pressure distillates,distillates resulting from the cracking of petroleum oils, or to thetreatment of straight run distillates from petroleum oils, all of whichI include in the term hydrocarbon oil.

The oils to be treated should be substantially free of undissolved waterwhen treated in accordance with the present invention, that is 'to say,the action of the metal compounds, adsorbent material, added oxygen andacid on the oils should take place substantially in the absence ofwater. If the oil before treatment in accordance with the presentinvention has been washed with water or treated with any aqueoussolution, the water, or aqueous solution should be allowed to completelysettle from the oil,-and the oil only when separated from water oraqueous solution used for practicing the invention. Preferably the souroils to be sweetened should be dried by passing them over or in contactwith drying agents as heretofore described. Small amounts of waterwithin the limits explained in precedingparagraphs of this descriptionare not objectionable, nor does any water which may be dissolved in theoil treated impair the operation of the process. The terms used in theappended claims are intended to cover and describe the processes definedtherein when practiced with water moisture contents in the oils andreagents employed ranging from zero per cent to the limits given in thisand preceding paragraphs of this-description.

Instead of utilizing the metal compounds such as cupric oxide, cuprichydroxide, cupric chloride, cupric nitrate, basic cupric carbonate,mercuric chloride, ferric chloride, ferric sulphate etc., in the highervalency in the beginning of the treat- ,ment of the oils to sweetenthem, these cornpounds may be employed in the beginning in the lowervalencies or in the -ous condition and brought up to the higher valencyor -ic condition during the practice of the invention through theoxidizing action of the oxidizing agent introduced into the oilundergoing treatment or through the oxidizing agents added to the metalcom;

, separate step. For example, referring to Figure 1 of the drawings,-the sour oils may first be treated with the sweetening reagents ormixtures of sweetening reagents and adsorbent material and after theyhave become partially or l5 wholly spent, the slurry of oil and thesweetening agents or the slurry of oil with the mixtures of sweeteningagents and absorbent material may be circulated in the apparatus shownin the drawings by means of the centrifugal pump while oxygen or air isadded thereto through the pipe 9 with or without the introduction ofhydrochloric acid through the pipe I0. Or the slurry of oil with thepartially or wholly spent metal compounds or mixtures of metal compoundsand clay may be withdrawn from the tank 2 and placed in anothercontainer and the said slurry intimately contacted with air or oxygen.with or without the intimate admixture thereto of hydrochloric acid. Itis, however, most advantageous to reactivate or maintain the activity ofthe sweetening agents or materials concurrently with the sweeteningoperation, because it has been found that the rate of regeneration ormaintenance of the activity of the sweetening agents is at least as fastas the rate of the sweetening action, that is, that the rate ofregeneration, or maintenance of the activity, of the metal compounds ormixtures of metal compounds and clay does not lag behind the rate ofsweetening of the sour constituents, as appears to be the case wherelarge quantities of water are present, and furthermore, the addedoxygen, as pointed out above, retards the forma-' tion of pellets andalso prevents objectionable colorations being produced in the oilstreated by the reagents employed.

Instead'of passing the air or oxygen into contact with the metalcompound and adsorbent while the sour oil is being treated as shown inFigure 2, the flow of the oil may be discontinued and air or oxygenblown or aspirated through the metal compound and adsorbent toregenerate them; or regeneration of the metal compound and adsorbent maybe accomplished by removing them from the apparatus and exposing them tothe air, while spread out in thin layers, for a the valve M in the pipe8 is closed. The batch so introduced is maintained in continuouscirculation in the apparatus in the manner described above in practicingthe process. When using the apparatus shown in Figure 2, a single batchof metal compound and adsorbent introduced into chamber 3| sufiices fortreating very large volumes of oil.

95% of the mixture.

pipe l2 of Figure 1 and the pipe 40 of Figure 2 are ready for use andsale, with the possible exception of the addition of a suitableinhibitor to retard'or prevent the formation of gums during periods oflong storage of the products sweetened. It is not necessary to subjectthe oils after they have been sweetened according to the presentinvention to washing with aqueous solutions of sodium hydroxide orsodium carbonate or other alkaline agent, nor is it necessary torevaporize or re-distil the sweetened oils for preparing them for finaluse, as they may be used and marketed substantially as they leave thetreaters shown in the drawings.

As indicated above the process in substance converts the sourconstituents of the oils or mercaptans into disulphides by oxidation.The materials used as treating agents act in substance as carriers foroxygen to the mercaptans, oxidizing them to disulphides, that is to sayas promoters of oxidation of the mercaptans. While I have enumerated anumber of metal compounds which may be used, itis to be understood thatI do not limit myself to the compounds or agents specificallyenumerated, as others are within the scope and principle of myinvention. A substantially dry mixture of lead oxide (litharge), sodiumhydroxide and adsorbent, for example, Iuller's earth, if intimatelymixed or contacted with sour gasoline or oil with intimate admixturewith the oil of oxygen or air, will sweeten sour oils and the presenceor addition of air or oxygen will maintain the sweetening activity ofthe mixture of lead oxide, sodium hydroxide and adsorbentfi In this lastmentioned instance, the substantially dry mixture of lead oxide, sodiumhydroxide and adsorbent may be employed in substantially. the same wayto sweeten the sour oils as the clay-cupric chloride mixture describedabove, except that no hydrochloric acid ls employed, and no sulphur isrequired to be added to the oils as is usual in employing sodiumplumbite. The litharge and sodium hydroxide may be employed about in theproportions that would form sodium plumbite and the fuller's earth maybe varied between wide limits, for example the fullers earth may formfrom 40% to In this latter example of reagents it may become necessaryto have a small amount of water moisture present to initiate thechemical actions, but water moisture should not be present to such anextent that the reagents acquire a muddy or plastic condition. Thus, Ido not limit the practice or scope of the invention to any particularagent or mixtures but the invention includes the use of all agents ormixtures operating within the principle of the invention, whether or notthe agents contain components capable of existing in different degreesof oxidation or valencies. 1

The terms oxygen and "gaseous 'oiwgen in the appended claims areintended to include,

wherever the context permits, oxygen in pure orimpure condition, andoxygen gas in admixture with other gases, for example air, which is amix agents which may contain the natural water content of the solidadsorbent and/or any normal water of crystallization of the inorganicsalts employed, and water incidentally formed in the process or taken upfrom the oil being treated, but wherein the moisture content of the saidtreating agents or mixtures is not suilicient to cause the formation ofan independent aqueous solution phase separable or flowable as such fromthe adsorbent material, or to cause the formation of an aqueous muddymass with the clay or other adsorbent, as indicated above in thespecification.

Due to the dehydrating effect of cracked gasolines which previously havebeen washed with caustic soda v(NaOH) solution and contacted thereafterwith solid sodium chloride or solid calcium chloride, it may becomenecessary, in practicing the present invention, to add to or'mix intothe oils entering the tank 2 or chamber 3|, a small or controlled amountof water moisture to accelerate the sweetening action or to promote thechemical actions occurring in said tank or chamber; but water limitsshould be maintained purities in the gasoline which appear to exercise aretarding influence upon the action of the sweetening agents used in thepresent invention. For this purpose one-per cent water solutions ofhydrochloric acid or sulphuric acid, or ten per cent water solution offerric chloride, may be employed. The hydrochloric acid, sulphuric acidor ferric chloride solution is intimately mixed or agitated withgasoline, whereupon the gasoline is separated from the aqueous solution,and the so treated and separated gasoline then treated according to thepresent invention.

When such pretreatment is applied to raw pressure distillates and saidso treated pressure distillates sweetened according to the presentinvention, the resulting sweetened gasoline has a better inductionperiod and exhibits a better gum test than such gasolines would exhibitif treated according to the present invention without such pretreatment.

The presint application is a continuation in part of my copendingapplications which have issued into Patents No. 2,042,054, May 26, 1936;No. 2,042,052, May 26, 1936; and No. 2,042,051, May 26, 1936.

I claim:

1. The process of treating sour hydrocarbon oil to sweeten same whichcomprises contacting said oil, in the presence of added oxidizing agent,with a substantially non-aqueous mixture com prising an adsorbentmaterial and a compound of copper which forms mercaptides withmercaptans, sad oxidizing agent having the property of prolonging theactivity of said mixture and being in addition to any oxygen initiallyoccluded in V the adsorbent material.

2. The process of treating sour hydrocarbon oil to sweeten same whichcomprises contacting sour hydrocarbon oil, substantially in the absenceof water, with cupric chloride in the presence of gaseous oxygen. 1

3. The process of treating sour hydrocarbon oil to sweeten same, whichcomprises contacting sour hydrocarbon oil, substantially in the absenceof water, with a substantially non-aqueous mixture comprising anadsorbent material and cupric chloride, and performing said contactingin the presence of an oxidizing agent which prolongs the activity ofsaid mixture, said oxidizing agent being in addition to any oxygeninitially occluded in the adsorbent material. I

4. The process of treating sour hydrocarbon oil to sweeten same whichcomprises contacting sour hydrocarbon oil, substantially in the absenceof water, with a substantially non-aqueous mixture comprising cupricchloride and an adsorbent material, and performing said contacting inthe presence of a mineral acid and oxygen other than any oxygen whichmay be initially occluded in said adsorbent material.

5. The process of treating sour. hydrocarbon oil to remove sournesswhich comprises contacting said oil, in, the presence of gaseous oxygenadded thereto, with a substantially dry mixture comprising an adsorbentmaterial and a salt of copper which forms mercaptides with mercaptans. K

6. The process of treating sour hydrocarbon oil to remove sourness whichcomprises contacting said oil, in the presence of gaseous oxygen addedthereto, with a substantially dry mixture comprising a chloride orcopper and an adsorbent material.

7. The process of treating sour hydrocarbon oil to remove sourness whichcomprises contacting said oil, at substantially an atmospherictemperature, in the presence of gaseous oxygen added thereto, with asubstantially dry mixture comprising an adsorbent material and acompound of copper which reacts with mercaptans to form mercaptides.

8. The process of treating sour hydrocarbon oil to remove sourness whichcomprises contacting said oil, at substantially an atmospherictemperature, in the presence of gaseous oxygen added thereto, with asubstantially dry mixture comprising an adsorbent material and a salt ofcopper which reacts with mercaptans to form mercaptides.

9. The process of treating sour hydrocarbon oil to remove sourness whichcomprises contacting said oil, at substantially an atmospherictemperature, in the presence of gaseous oxygen added thereto, with asubstantially dry mixture comprising a chloride of copper and anadsorbent material.

10. The process of treating sour hydrocarbon oil to remove sournesswhich comprises contacting said sour oil, at a temperature below thepoint at which mercaptides are decomposed by heat, with a substantiallydry mixture comprising an adsorbent material and a compound of copperwhich reacts with mercaptans to form mercaptides, contacting saidmixture with gaseous oxygen to revivify it, and contacting furtherquantitles of sour hydrocarbon oil with said revivified mixture tosweeten said oil.

11. The process of treating sour hydrocarbon oil to sweeten same, whichcomprises subjecting .sald sour oil, incorporated with gaseous oxygen,

bon oil which comprises contacting said oil at? 10 substantially anatmospheric temperature, and

substantially in the absence of water, witha mix-" -ture comprising anadsorbent material and a salt of a metal exhibiting variable valencyforming mercaptides with mercaptans, and subjecting said mixture to theactlon'of an oxidizing agent which regenerates said mixture, andcontacting further quantities of sour oil with the regenerated mixture.

14. In the treatment of sour hydrocarbon oil which has been previouslytreated to remove water therefrom, the process which comprisesincorporating an oxygen containing gas in the said sour oil, andsubjecting the resultant mixture to the action of (1) a solid salt ofametal which reacts with sour constituents in the oil to form organicsulphur metal compounds, and which is maintained active in the presenceof oxygen, and (2) an adsorbent material.

15. The process of treating sour hydrocarbon oil to sweeten same whichcomprises contacting said oil, substantially in the absence of water,and at substantially an atmospheric temperature. with a mixturecomprising an adsorbent material and a salt forming with sourconstituents in said oil organic sulphur metal compounds removable fromsaid oil by the adsorbent material, and conducting said contacting inthe presence of an added oxidizing agent which imparts renewed activityto said mixture for sweetening further quantitiesof sour oil, said addedoxidizing agent being in addition to any joxygen occluded in saidadsorbent material originally.

16. The process of treating sour hydrocarbon oil to sweeten same whichcomprises contacting said oil, substantially in the absence" of water,with a mixture comprising an adsorbent material and a salt forming withsour constituents in said oil organic sulphur metal compounds removablefrom said oil by the adsorbent material, and, at V least during a partof the time of said contacting adding to the oil undergoing treatment anoxidizing agent which revivifies the activity of said mixture to sweetenfurther quantities of sour oil, said oxidizing agent being in additionto any oxygen which may be occluded in said adsorbent material at thebeginning of the treatment.

17. In the treatment of sour hydrocarbon oil which previously has beentreated to remove hydrogen sulphide and water therefrom, the processwhich comprises incorporating in the said sour oil gaseous oxygen, andsubjecting the resultant mixture to the action of (1) a solid salt of ametal which reacts with sour constituents in the oil to form organicsulphur metal compounds, and which is maintained active in the presenceof the said oxygen, and (2) an adsorbent material.

18. The process of treating asour hydrocarbon oil to decomposemercaptans contained therein which comprises reacting upon mercaptanscontained in said sour oil with a salt to form mercaptides, forming saidmercaptidcs in the presence of an adsorbent material substantially freeof water, so that said mercaptides can come into contact with saidadsorbent material, and after 75 said contact subjecting said adsorbentmaterial to the action of oxygen, and thereafter contacting furtherquantities of sour oil with the said so treated adsorbent material tosweeten said sour oil.

contacting said oil with a dry mixture comprising V an adsorbentmaterial and a salt which reacts with sour constituents in the oil andsweetens the oil in the presence of said adsorbent material, said salthaving also the property of being regenerated for repeated used in saidmixture upon being contacted in said mixture with elemental oxygen, thesaid contact with said mixture being performed at a temperature belowthe point at which mer captides are decomposed by heat, subjecting thesaid mixture after use in sweetening sour oil to the. action of anoxidizing agent which regenerates the sweetening powers of said mixture,and contacting further quantities of sour oil with said so regeneratedmixture to sweeten same.

21. The process of treating sour hydrocarbonoil to sweeten same whichcomprises contacting said oil with a dry mixture comprising adsorbentmaterial and a salt which reacts with sour constituents in the oil andsweetens the oil in the presence of said adsorbent material, said salthaving also the property of being maintained in activity for repeateduse in 'said mixture for sweetening sour oil upon being'contacted insaid mixture with elemental oxygen, and adding to the oil undergoingcontact with said mixture, at least during a portion of the time the oilis undergoing contact therewith, an oxidizing-agent which maintains thesweetening activity of said mixture.

22. The process of treating sour hydrocarbon oil to remove sourconstituents, which comprises removing hydrogen sulphide from said souroil, contacting the thus treated oil with dry treating agents comprisinga compound of a metal forming organic sulphur metal compounds withsubstances in the oil imparting sourness thereto, and whichmetalcompound is maintained active in the presence of oxygen, and anadsorbent material, the said contacting step being conducted in thepresence of an added gaseous oxidizing agent which maintains thesweetening activity of the said agents.

23. In the treatment 'of sour hydrocarbon oil for sweetening the same,which oil has been 19. The process of treating a sour hydrocarbon and(2) an adsorbent material.

treated to remove water, the process which com-' prises contacting thethus treated oil with a compound of a metal forming organic sulphurmetal compounds with substances in the oil imparting sourness thereto,and which metal compound is maintained active in -the presence ofoxygen, and with an adsorbent material, the said contacting step beingconducted in the presence of an added gaseous oxidizing agent whichmaintains the sweetening activity of the said treating agents.

24. In the treatment ofsour hydrocarbon oil to remove sourness, whichoil previously has beentreated to remove water therefrom, the processwhich comprises contacting the thus treated oil with a substantially drymixture comprising an adsorbent material and a compound of a metalforming organic sulphur metal compounds with compounds in the oilimparting sourness'thereto and which is maintained active in thepresence of oxygen, the said contacting step being conducted ,in thepresence of added oxygen which maintains the sweetening activity of saidmixture. 25. A process according to claim 21 in which the oiliscontacted with the mixture defined in remove mercaptides from saidoil.

'27. Process for sweetening mercaptan-bearing hydrocarbon oil, whichcomprises adding to said oil asmall controlled amount of water moistureand a gas containing free oxygen, and contacting the resultant mixturewith (1) a salt of a metal which reacts with mercaptans in the presenceof free oxygen to form mercaptides and which salt is maintained activein the presence of oxygen,

28. Process for sweetening a sour hydrocarbon oil that has dehydratingproperties, which comprises contacting said oil containing free oxygenwith a sweetening agent comprising an adsorbent material and cupricchloride, and introducing controlled amounts of water moisture into theoil flowing to the sweetening agent, thereby counteracting thedehydrating effect of said hydrocarbon oil upon said mixture andaccelerating sweetening of the oil.

29. Process for sweetening mercaptan-bearing hydrocarbon oil to sweetenthe same, which comprises adding to said oil an oxygen-containinggas anda controlled amount of moisture, and contacting the resultant mixturewith a treating agent comprising an'adsorbent' material and a coppercompoundforming mercaptides with mercaptans. a

30. Process as defined in claim 29, wherein said copper compound iscupric chloride.

CHARLES O. HOOVER.

